Unique phenomena in SnO2-based gas sensing devices exposed to ammonia gas

Gas detection characteristics for NH₃ gas have been studied for SnO₂ mixed with ZrO₂ and hydrophilic silica. Both an increase and a decrease in device conductivity can be obtained when the device is exposed to NH₃ gas independently of the device temperature. This unique feature is exhibited when the device temperature is kept above 260°C. For a device mixed with 1 wt% hydrophilic silica, especially, a remarkable decrease in conductivity has been observed at 370°C device temperature. It is also found that this property can be utilized to make a highly selective NH₃ gas detector, since the conductivity of SnO₂-based devices usually increased for other reducing gases. Oscillation phenomena are also observed in devices mixed with 5 wt% hydrophilic silica at 370°C device temperature and 200 ppm NH₃ concentration. The oscillation period varies from 4 to 20 min and the amplitude varies from 2 × 10^?8 to 11 × 10^?8 mho.     

Characteristics of Pd-doped tin oxide ceramics in response to CO gas

The CO response of Pd-doped tin oxide ceramics in both pellet and thick film versions is investigated. The porous thick film samples exhibit more sensitive CO response than pellet ones. A linear relation between CO concentration and sample resistance change is observed for samples doped with one wt.% PdCl₂, while semi-logarithmic relations are obtained for samples doped with 2, 3 and 5 wt.% PdCl₂. An optimum PdCl₂ content of 2 wt.% yields the best response to CO gas. The existence of the optimum catalyst content is attributed to a synergistic reaction. A possible mechanism for the CO sensing of tin oxide ceramics is explored.     

Co gas detection by ThO2-Doped SnO2

The selective detection of CO gas by stannic oxide incorporated with ThO2(l − 10 wt%), in the presence of H2 and petroleum gases such as C₃H₈ and iso-C₄H₂ has been studied. Materials mixed with 5 wt% ThO₂ showed high selectivity to CO gas at a sample temperature of 200−250‡C. The effects of hydrophobic or hydrophilic silica present in the samples on the detection sensitivity to CO gas have been investigated. From the results it is apparent that the removal of the hy-droxyl radical from the surface of SnO₂ enhances the sensitivity to CO gas.     

SnO_2基CO气敏材料的制备与掺杂研究

以溶胶–凝胶法制备的SnO2纳米材料为基,采用Sb2O3掺杂改性,制备出CO气敏材料。用XRD分析了材料的结构、物相和颗粒度。通过同步TGA/DSC热重分析的方法分析了材料的稳定性。结果表明:掺入w(Sb2O3)为2%时,可以抑制晶粒度的长大,同时提高了材料的稳定性。工作温度在90~110℃变化时,气敏元件电阻值波动不大((R10R20) /R10= 12%)。R10和R20分别表示元件在空气中90℃和110℃时的阻值。     

Temperature dependence of Rresistivities of SnO2-based gas sensors exposed to Co,H2, and C3H8 gases

The temperature dependence of resistivities of gas sensors made of SnO₂, Pd-doped SnO₂, and ThO₂-doped SnO₂ with Pd has been investigated in air containing reducing gases such as CO, H₂, and C₃H₈. The curves for ThO₂-doped sensors were significantly influenced by the reducing gases as compared to the sensors without ThO₂. From these results, it is found that in Pd-doped SnO₂ sensors the dopant plays an important role in oxidizing the surface of SnO₂ above 170°C, and that the addition of ThO₂ to Pd-doped SnO₂ enhances the effects of Pd by removing the adsorbed hydroxyl on SnO₂. It is also apparent that the interactions between reducing gases in air and SnO₂-based sensors depend upon the oxidizing rates of the surface of SnO₂, as well as the amounts of the adsorbed hydroxyl on SnO₂.     

基于La0.7Sr0.3FeO3的微结构乙醇气体传感器的研制

以La_0.7Sr_0.3FeO₃为敏感材料，设计制成了一种新型的共平面结构气体传感器.基于有限元分析软件Ansys对该传感器结构进行了优化设计.实验测得该传感器对于500ppm浓度乙醇气体的灵敏度为8.0，功耗为261mW，是同种敏感材料烧结型传感器功耗的2/3，响应时间约为1.5s，恢复时间约为2.5s，是一种功耗低、灵敏度高、稳定性好的微结构乙醇气体传感器.     

基于石墨烯的CO和CO2气体传感器研究进展

室温下石墨烯具有电子迁移率高、比表面积大、机械强度高、化学稳定性和热稳定性优异、导电性好等独特性能,是当今最受关注的二维材料之一。与传统无机氧化物材料相比,石墨烯气体传感器具有工作温度低、能耗小、恢复性高的优点。文章对两种石墨烯气体传感器的研究进展进行了综述。根据气体选择性不同,将石墨烯气体传感器分为检测CO和CO₂气体传感器。分别对其灵敏度、气体响应灵敏度和响应时间等特性进行分析对比。此研究对此类传感器的应用与推广具有一定的指导意义。     

Microstructure and Characteristics of Thin-Film La<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>Co<Subscript>0.5</Subscript>Ni<Subscript>0.5</Subscript>O<Subscript>3</Subscript>/ZnO:Al Heterocontact CO Sensors Prepared by RF Magnetron Sputtering

Highly sensitive CO gas sensors based on heterocontacts of ZnO:Al on La_0.8Sr_0.2Co_0.5Ni_0.5O₃ (LSCNO) were fabricated successfully. La_0.8Sr_0.2Co_0.5Ni_0.5O₃ thin films were coated on (100) silicon wafers by a sol-gel method including the Pechini process followed by a spin-coating procedure. Then, ZnO:Al films prepared by radiofrequency (RF) magnetron sputtering at various oxygen partial pressures and deposited on as-deposited La_0.8Sr_0.2Co_0.5Ni_0.5O₃ films were investigated. The results revealed that the CO sensing ability of the film prepared with the ratio of O₂/Ar = 5/5 (ratio of volume flow rate) was the worst, owing to the highest (002) plane orientation in the ZnO:Al film. In contrast, the ZnO:Al film prepared with O₂/Ar = 3/7 exhibited better CO sensitivity. Furthermore, all two-layer samples showed higher CO sensitivities than single-layer samples. The CO sensitivity of ZnO:Al/La_0.8Sr_0.2Co_0.5Ni_0.5O₃ thin film was 45% for 500 ppm CO at a sensing temperature of 200°C.     

Synthesis of New RuO2@SiO2 Composite Nanomaterials and their Application as Catalytic Filters for Selective Gas Detection

RuO₂@SiO₂ nanomaterials are prepared using hybrid mesostructured silica (EtO)₂P(O)(CH₂)₃SiO_1.5/x SiO₂ (x = 9, 16) by anchoring the metal precursor [Ru(COD)(COT)] (COD is 1,3‐cyclooctadiene, COT is 1,3,5‐cyclooctatriene) inside the pores of the organized silica matrix through the phosphonate moieties. Following this task, the nanoparticles are fabricated by i) decomposing the metal precursor with hydrogen at room temperature in tetrahydrofuran to achieve ruthenium nanoparticles and ii) thermally treating the ruthenium particles in silica at 450 °C in air to fabricate RuO₂. The materials containing Ru and RuO₂ nanoparticles are characterized by elemental analysis, transmission electron microscopy (TEM), X‐ray diffraction (XRD), nitrogen sorption measurements, and ³¹P and ¹³C NMR. The obtained RuO₂@SiO₂ nanomaterials are evaluated as catalytic filters when deposited onto gas sensors for the preferential detection of propane in the multicomponent gas mixture propane/carbon monoxide/nitrogen dioxide.     

Highly concentrated ozone gas supplied at an atmospheric pressure condition as a new oxidizing reagent for the formation of SiO2 thin film on Si

We have investigated the characteristics of silicon oxidation by concentrated ozone gas through the comparison of the oxidation by oxygen molecules. A sophisticated high-concentration ozone generator, which exploits the ozone/oxygen gas separation technique with silica gel, has been developed for the study. The generator can continuously supply ozone-oxygen mixtures with ozone concentrations up to 30 at.% at one atmospheric pressure. Ozone gas with a concentration of 25 at.% from the generator formed SiO₂ films as thick as 2 nm and 6 nm on Si for a 30 min. exposure at 200°C and 600°C, respectively. On the other hand, oxygen gas by itself could form SiO₂ films with only 1 nm and 3 nm thickness, respectively, at the same conditions. Moreover, in the oxide film formation at 600°C, the oxide film growth by ozone was proceeded with an oxidation time in excess of 240 min., while it saturated within very short time in the oxidation by oxygen. These phenomena verify the strong oxidation power of ozone. In addition, we confirmed that the growth rate of the silicon oxide with ozone dramatically changed when the substrate temperature was over 500°C, and this suggested the change of oxidation mechanism at this point. However, such a characteristic was not found in oxidation with oxygen.     

掺杂改善SnO_2甲醛气敏元件灵敏度特性的研究

用纳米SnO2制作了旁热式气敏元件。用掺杂方法提高SnO2甲醛气敏元件的灵敏度,掺杂剂包括Pd,Sb,Ti,Zr,Cu,Ag,Mn等。在SnO2气敏元件中分别掺杂质量分数2%Pd和2%Zr对提高元件灵敏度有显著效果。未掺杂SnO2、掺杂质量分数2%Pd和2%Zr的气敏元件对体积分数为5×10-5甲醛的灵敏度分别为1.33,2.38,2.08,但是掺杂在改善元件对乙醇的选择性方面作用不大。分析了掺杂改善SnO2气敏元件灵敏度的原理,当SnO2表面吸附还原性气体时,吸附气体提供电子,使半导体表层的导电电子数增加,引起电导率增加、电阻下降。吸附气体浓度越高,电阻率变化越大,元件灵敏度越大。     

Low‐Temperature Growth of SnO2 Nanorod Arrays and Tunable n–p–n Sensing Response of a ZnO/SnO2 Heterojunction for Exclusive Hydrogen Sensors

Uniform SnO₂ nanorod arrays have been deposited at low temperature by plasma‐enhanced chemical vapor deposition (PECVD). ZnO surface modification is used to improve the selectivity of the SnO₂ nanorod sensor to H₂ gas. The ZnO‐modified SnO₂ nanorod sensor shows a normal n‐type response to 100 ppm CO, NH₃, and CH₄ reducing gas whereas it exhibits concentration‐dependent n–p–n transitions for its sensing response to H₂ gas. This abnormal sensing behavior can be explained by the formation of n‐ZnO/p‐Zn‐O‐Sn/n‐SnO₂ heterojunction structures. The gas sensors can be used in highly selective H₂ sensing and this study also opens up a general approach for tailoring the selectivity of gas sensors by surface modification.     

纳米氧化钨薄膜改性的大孔硅气敏传感器

通过双槽电化学腐蚀法在P型单晶硅表面制备了大孔硅。然后通过直流对靶反应磁控溅射法在大孔硅表面淀积了纳米氧化钨薄膜。使用场发射扫描电子显微镜（FESEM）观察大孔硅和氧化钨/大孔硅样品的形貌。分别使用X射线衍射（XRD）图谱和X射线光电子能谱（XPS）分析氧化钨晶体结构和钨的化合价。在室温下测试大孔硅和氧化钨/大孔硅气敏传感器的气敏特性。结果表明：氧化钨/大孔硅气敏传感器表现出了P型半导体气敏传感器的气敏特性。它对1ppm的二氧化氮显示了良好的恢复特性和重复性。氧化钨/大孔硅气敏传感器的长期稳定性要好于大孔硅气敏传感器。氧化钨的添加提高了大孔硅气敏传感器对二氧化氮的灵敏度。氧化钨/大孔硅气敏传感器对于二氧化氮的灵敏度要高于其对氨气和乙醇的灵敏度。通过淀积纳米氧化钨薄膜,改善了大孔硅对二氧化氮的选择性。     

Thick-film CO gas sensors

A gas sensor of SnO2-based materials has been made by thick-film technology utilizing hydrophobic silica as a binder. The technology can achieve a high productivity as well as a reduced humidity dependence and a sufficient mechanical strength of sensors. A thick-film sensor of SnO2incorporated with ThO2shows highly selective detection for CO gas, separated from H2gas; i.e., sensitivity to CO is 42 times higher than to H2at both gas concentrations of 50 ppm. An excellent humidity-independent sensitivity is also achieved.     

MQS1型一氧化碳气敏元件

氧空位与材料的气敏特性有着密切的关系，气敏材料的电导率由氧空位的形成和氧化过程共同决定，氧空位浓度越大，气敏效应越明显。根据氧化锡的这一气敏机理，以９９．９９％的锡为原料，掺入合适的添加剂，制成了ＭＱＳ１型一氧化碳气敏元件。它的灵敏度高、选择性好、响应恢复快、受温度和湿度的影响小。     

The Role of NiO Doping in Reducing the Impact of Humidity on the Performance of SnO2‐Based Gas Sensors: Synthesis Strategies,and Phenomenological and Spectroscopic Studies

The humidity dependence of the gas‐sensing characteristics in SnO₂‐based sensors, one of the greatest obstacles in gas‐sensor applications, is reduced to a negligible level by NiO doping. In a dry atmosphere, undoped hierarchical SnO₂ nanostructures prepared by the self‐assembly of crystalline nanosheets show a high CO response and a rapid response speed. However, the gas response, response/recovery speeds, and resistance in air are deteriorated or changed significantly in a humid atmosphere. When hierarchical SnO₂ nanostructures are doped with 0.64–1.27 wt% NiO, all of the gas‐sensing characteristics remain similar, even after changing the atmosphere from a dry to wet one. According to diffuse‐reflectance Fourier transform IR measurements, it is found that the most of the water‐driven species are predominantly absorbed not by the SnO₂ but by the NiO, and thus the electrochemical interaction between the humidity and the SnO₂ sensor surface is totally blocked. NiO‐doped hierarchical SnO₂ sensors exhibit an exceptionally fast response speed (1.6 s), a fast recovery speed (2.8 s) and a superior gas response (R_a/R_g = 2.8 at 50 ppm CO (R_a: resistance in air, R_g: resistance in gas)) even in a 25% r.h. atmosphere. The doping of hierarchical SnO₂ nanostructures with NiO is a very‐promising approach to reduce the dependence of the gas‐sensing characteristics on humidity without sacrificing the high gas response, the ultrafast response and the ultrafast recovery.     

基于石墨烯的NO2和NH3气体传感器研究进展

室温下石墨烯具有较大的分子吸附比表面积、低噪声、高载流子迁移率等优异电学性能,是一种性能极佳的传感材料。与传统无机氧化物气体传感器相比,石墨烯气体传感器具有工作温度低、能耗小、恢复性高的优点。文章对两种石墨烯气体传感器的研究进展进行了综述。首先根据气体选择性不同,研究了NO₂和NH₃两种石墨烯气体传感器。然后对它们的灵敏度、气体响应灵敏度、响应时间等特性进行了分析对比。该项分析研究工作对气体传感器的实际应用与推广具有一定参考价值。     

High Performance Three‐Dimensional Chemical Sensor Platform Using Reduced Graphene Oxide Formed on High Aspect‐Ratio Micro‐Pillars

The sensing performance of chemical sensors can be achieved not only by modification or hybridization of sensing materials but also through new design in device geometry. The performance of a chemical sensing device can be enhenced from a simple three‐dimensional (3D) chemiresistor‐based gas sensor platform with an increased surface area by forming networked, self‐assembled reduced graphene oxide (R‐GO) nanosheets on 3D SU8 micro‐pillar arrays. The 3D R‐GO sensor is highly responsive to low concentration of ammonia (NH₃) and nitrogen dioxide (NO₂) diluted in dry air at room temperature. Compared to the two‐dimensional planar R‐GO sensor structure, as the result of the increase in sensing area and interaction cross‐section of R‐GO on the same device area, the 3D R‐GO gas sensors show improved sensing performance with faster response (about 2%/s exposure), higher sensitivity, and even a possibly lower limit of detection towards NH₃ at room temperature.     

Encapsulation of Semiconductor Gas Sensors with Gas Barrier Films for USN Application

Sensor nodes in ubiquitous sensor networks require autonomous replacement of deteriorated gas sensors with reserved sensors, which has led us to develop an encapsulation technique to avoid poisoning the reserved sensors and an autonomous activation technique to replace a deteriorated sensor with a reserved sensor. Encapsulations of In₂O₃ nanoparticles with poly(ethylene‐co‐vinyl alcohol) (EVOH) or polyvinylidene difluoride (PVDF) as gas barrier layers are reported. The EVOH or PVDF films are used for an encapsulation of In2O3 as a sensing material and are effective in blocking In2O3 from contacting formaldehyde (HCHO) gas. The activation process of In2O3 by removing the EVOH through heating is effective. However, the thermal decomposition of the PVDF affects the property of the In₂O₃ in terms of the gas reactivity. The response of the sensor to HCHO gas after removing the EVOH is 26%, which is not significantly different with the response of 28% in a reference sample that was not treated at all. We believe that the selection of gas barrier materials for the encapsulation and activation of In2O3 should be considered because of the ill effect the byproduct of thermal decomposition has on the sensing materials and other thermal properties of the barrier materials.     

Low-temperature carbon monoxide gas sensors based gold/tin dioxide

Tin dioxide nanocrystals were synthesized by a precipitation process and then used as the support for 2 wt.% gold/tin dioxide preparation via a deposition–precipitation method, followed by calcination at 200 °C. Thick films were fabricated from gold/tin dioxide powders, and the sensing behavior for carbon monoxide gas was investigated. The gold/tin dioxide was found to be efficient carbon monoxide gas-sensing materials under low operating temperature (83–210 °C). The Au/SnO₂ sensor with SnO₂ calcined at 300 °C exhibited better CO gas-sensing behavior than the SnO₂ calcined at other temperatures. The experimental results indicated the potential use of Au doped SnO₂ for CO gas sensing.